WO2015152058A1 - Composition d'électrolyte polymère, membrane électrolytique polymère l'utilisant, membrane électrolytique revêtue d'une couche de catalyseur, ensemble membrane-électrodes et pile à combustible à électrolyte polymère solide - Google Patents

Composition d'électrolyte polymère, membrane électrolytique polymère l'utilisant, membrane électrolytique revêtue d'une couche de catalyseur, ensemble membrane-électrodes et pile à combustible à électrolyte polymère solide Download PDF

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WO2015152058A1
WO2015152058A1 PCT/JP2015/059661 JP2015059661W WO2015152058A1 WO 2015152058 A1 WO2015152058 A1 WO 2015152058A1 JP 2015059661 W JP2015059661 W JP 2015059661W WO 2015152058 A1 WO2015152058 A1 WO 2015152058A1
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electrolyte membrane
polymer electrolyte
polymer
catalyst layer
ionic group
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PCT/JP2015/059661
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English (en)
Japanese (ja)
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國田友之
出原大輔
梅田浩明
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東レ株式会社
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Priority to EP15774165.3A priority Critical patent/EP3128592B1/fr
Priority to KR1020167028592A priority patent/KR102282248B1/ko
Priority to JP2015519115A priority patent/JP6610252B2/ja
Priority to US15/301,018 priority patent/US10253147B2/en
Priority to CN201580017524.4A priority patent/CN106133976B/zh
Priority to CA2944372A priority patent/CA2944372C/fr
Publication of WO2015152058A1 publication Critical patent/WO2015152058A1/fr

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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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Definitions

  • the present invention relates to a polymer electrolyte composition, a polymer electrolyte membrane, a catalyst layer-covered electrolyte membrane, a membrane electrode assembly, and a solid polymer fuel cell.
  • a fuel cell is a kind of power generation device that extracts electric energy by electrochemically oxidizing a fuel such as hydrogen or methanol, and has recently attracted attention as a clean energy supply source.
  • the polymer electrolyte fuel cell has a standard operating temperature as low as around 100 ° C. and a high energy density, so that it is a relatively small-scale distributed power generation facility, a mobile power generator such as an automobile or a ship.
  • a mobile power generator such as an automobile or a ship.
  • secondary batteries such as nickel metal hydride batteries and lithium ion batteries.
  • an anode electrode and a cathode electrode in which a reaction responsible for power generation occurs, and a polymer electrolyte membrane serving as a proton conductor between the anode and the cathode are sometimes referred to as a membrane electrode assembly (hereinafter, abbreviated as MEA).
  • MEA membrane electrode assembly
  • a cell in which this MEA is sandwiched between separators is configured as a unit.
  • the main component of the polymer electrolyte membrane is an ionic group-containing polymer (polymer electrolyte material), but it is also possible to use a polymer electrolyte composition containing an additive or the like in order to enhance durability.
  • the polymer electrolyte composition is also suitable as a binder for an electrode catalyst layer used in a particularly severe oxidizing atmosphere.
  • the required characteristics of the polymer electrolyte membrane and the polymer electrolyte composition include firstly high proton conductivity, and it is particularly necessary to have high proton conductivity even under high temperature and low humidification conditions.
  • the polymer electrolyte membrane and the polymer electrolyte composition serve as a barrier that prevents direct reaction between the fuel and oxygen, low fuel permeability is required.
  • Nafion registered trademark
  • DuPont which is a perfluorosulfonic acid polymer
  • Nafion registered trademark
  • DuPont which is a perfluorosulfonic acid polymer
  • the softening point is low and it cannot be used at a high temperature, and further, the problem of disposal after use and the difficulty of recycling materials are pointed out.
  • development of hydrocarbon-based electrolyte membranes has recently been activated as an inexpensive polymer electrolyte membrane that can replace Nafion (registered trademark) and has excellent membrane characteristics.
  • any of these polymer electrolyte membranes has a problem of insufficient chemical stability when used in a polymer electrolyte fuel cell.
  • the mechanism of chemical degradation has not been fully elucidated, but hydrogen peroxide generated mainly at electrodes during power generation, and hydroxy radicals generated by the reaction of the hydrogen peroxide with iron ions and copper ions in the film
  • the polymer chain and the side chain may be cut, and the polymer electrolyte membrane may become thin or fragile.
  • the polymer electrolyte membrane that has become fragile is damaged while it repeatedly swells and contracts in accordance with changes in humidity.
  • Patent Document 1 discloses that a perfluorosulfonic acid polymer is a polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) which is a sulfur-containing polymer and a polybenzimidazole (hereinafter abbreviated as PBI) which is a nitrogen-containing polymer.
  • PPS polyphenylene sulfide
  • PBI polybenzimidazole
  • Patent Document 2 proposes a polymer electrolyte composition in which a polyamic acid or a polyimide is blended with a perfluorosulfonic acid polymer or a sulfonic acid group-containing polyether ketone polymer (hereinafter sometimes abbreviated as sPEK). Yes.
  • Patent Document 3 proposes a polymer electrolyte composition in which perfluorosulfonic acid polymer or sPEK is mixed with insoluble PBI particles.
  • Patent Document 1 long-term durability is still insufficient.
  • Patent Document 2 suppresses methanol permeation by mixing polyamic acid and performing heat treatment, but both power generation performance and long-term durability are insufficient.
  • Patent Document 3 discloses that although the durability of the polymer electrolyte composition can be improved to some extent by decomposing hydrogen peroxide and hydroxy radicals by adding PBI, in terms of long-term durability. It was still inadequate.
  • the polymer electrolyte composition according to the prior art is insufficient as a means for improving economy, workability, proton conductivity, mechanical strength, chemical stability, and physical durability, and is industrially useful. It was not possible to become a polyelectrolyte composition.
  • the present invention has excellent chemical stability that can withstand a strong oxidizing atmosphere during fuel cell operation, and also has excellent proton conductivity and excellent mechanical strength under low humidification conditions.
  • a practically useful polymer electrolyte composition capable of achieving physical durability, and a polymer electrolyte membrane, a catalyst layer-covered electrolyte membrane, a membrane electrode composite, and a solid polymer fuel cell using the same It is to be provided.
  • a polymer electrolyte composition by containing an ionic group-containing polymer, a compound having an azole ring, and a specific transition metal-containing additive.
  • Products, especially polymer electrolyte membranes for fuel cells and membrane electrode composites, including proton conductivity and power generation characteristics including low humidification conditions, processability such as film forming properties, oxidation resistance, radical resistance, and hydrolysis resistance In addition to investigating that it is possible to express excellent performance in physical stability such as chemical stability, membrane mechanical strength, hot water resistance, etc. completed.
  • the polymer electrolyte composition of the present invention is a polymer electrolyte composition containing an ionic group-containing polymer (A), a compound having an azole ring (B), and a transition metal-containing additive (C),
  • the transition metal is at least one selected from the group consisting of cobalt, nickel, ruthenium, rhodium, palladium, silver and gold.
  • the present invention has excellent chemical stability that can withstand a strong oxidizing atmosphere during fuel cell operation, and also has excellent proton conductivity under low humidification conditions, excellent mechanical strength and physical durability. It is possible to provide a polymer electrolyte composition having excellent practicality, and a polymer electrolyte membrane, a catalyst layer-covered electrolyte membrane, a membrane electrode assembly, and a solid polymer fuel cell using the same.
  • (M1) to (M4) are explanatory views schematically showing aspects of a phase separation structure in a polymer electrolyte membrane, wherein (M1) is co-continuous, (M2) is lamellar, and (M3) is a cylinder structure. , (M4) illustrates a sea-island structure.
  • the compound (B) having an azole ring is a compound having at least one azole ring in the molecule.
  • the azole ring is a hetero five-membered ring containing one or more nitrogen atoms in the ring.
  • the hetero five-membered ring may contain atoms such as oxygen and sulfur other than nitrogen as hetero atoms other than carbon.
  • azole ring for example, in addition to a pyrrole ring containing only one nitrogen atom as a hetero atom other than a carbon atom, those having two hetero atoms other than a carbon atom include imidazole (1,3-diazole). ) Ring, oxazole ring, thiazole ring, selenazole ring, pyrazole (1,2-diazole) ring, isoxazole ring, isothiazole ring, etc.
  • imidazole ring imidazole ring, oxazole ring, thiazole ring, selenazole ring, 1H-1,2,3-triazole (1,2,3-triazole) ring, 1H-1, A 2,4-triazole (1,2,4-triazole) ring is preferable, and an imidazole ring is more preferable because it is easy to synthesize and can be used at low cost.
  • the azole ring as described above may be condensed with an aromatic ring such as a benzene ring, for example, p-phenylene group, m-phenylene group, naphthalene group, diphenylene ether group, diphenylene sulfone group, From the viewpoint of obtaining heat resistance, it is preferable to use a compound in which a divalent aromatic group such as a biphenylene group, a terphenyl group, or a 2,2-bis (4-carboxyphenylene) hexafluoropropane group is bonded to a hetero five-membered ring. .
  • the compound (B) having an azole ring is preferably a polyazole compound from the viewpoints of chemical stability and elution resistance.
  • polyazole compounds include polyimidazole compounds, polybenzimidazole compounds, polybenzobisimidazole compounds, polybenzoxazole compounds, polyoxazole compounds, polythiazole compounds, polybenzothiazole compounds, and the like. Examples include coalescence, but are not particularly limited.
  • polybenzimidazole compounds polybenzbisimidazole compounds, polybenzoxazole compounds, and polybenzthiazole compounds are preferable from the viewpoint of heat resistance and processability, and are easy to synthesize and used at low cost. Therefore, a polybenzimidazole compound is more preferable.
  • a macrocyclic compound is also preferable from the viewpoint of chemical stability and elution resistance.
  • the macrocyclic compound include compounds having a choline skeleton, a porphyrin skeleton, and a phthalocyanine skeleton, and compounds having an azacalixarene skeleton.
  • choline, porphyrin, protoporphyrin, phthalocyanine, corrole, chlorin, bacteriochlorin, coproporphyrinogen I, coproporphyrinogen III, uroporphyrinogen I, uroporphyrinogen III, protoporphyrinogen IX , Azacalixarene and the like but are not particularly limited.
  • choline, porphyrin, phthalocyanine, and azacalixarene are preferably used from the viewpoint of production cost, and porphyrin and phthalocyanine are more preferably used from the viewpoint of metal inactivation ability.
  • the trivalent nitrogen atom contained in the compound (B) having an azole ring is oxidized to a pentavalent N-oxide to function as a peroxide decomposing agent.
  • the nitrogen atom portion functions as a ligand for metal ions (Fe 2+ , Cu 2+, etc.) and functions as a metal deactivator that is deactivated by forming a strong complex.
  • the ionic group-containing polymer (A) and the compound having an azole ring (B) are uniformly mixed.
  • the ionic group-containing polymer (A) and the compound (B) having an azole ring are not uniformly mixed, that is, when having a phase separation structure, the swelling / contraction of the polymer electrolyte composition during fuel cell operation In some cases, delamination occurs at the interface portion of the phase separation structure, and the durability is lowered due to breakage starting from this.
  • the compound (B) having an azole ring and the ionic group-containing polymer (A) are in contact with each other only at the interface portion of the phase separation, the effect of the present invention cannot be sufficiently obtained.
  • the polymer electrolyte membrane described later when a block copolymer is used as the ionic group-containing polymer (A) and the polymer electrolyte membrane described later has a phase separation structure such as co-continuous or lamellar, the ionic group
  • the compound (B) having an azole ring is uniformly mixed with the compound (B) having an azole ring in any phase of the phase-separated ionic group-containing polymer (A) ( B) shall not be phase separated.
  • ionic group-containing polymer (A) and the compound (B) having an azole ring are uniformly mixed can be confirmed by the following method.
  • TEM transmission electron microscope
  • the shape of the island phase includes a circle, an ellipse, a polygon, and an indefinite shape.
  • the contrast of the black island particles is mainly caused by the compound (B) having an azole ring
  • the white sea (continuous phase) part is mainly caused by the ionic group-containing polymer (A).
  • the island phase (island particles) has a maximum length of 2 nm or more, and if it has only a size smaller than that, it is determined that it is uniformly mixed.
  • the sea phase may have a white and gray co-continuous or lamellar phase separation structure depending on the structure of the polymer and the contrast of TEM observation.
  • the compound (B) having an azole ring used in the present invention is a hydrocarbon solvent such as hexane, benzene, toluene, xylene, methanol, ethanol, isopropyl alcohol from the viewpoint of ease of processing and suppression of formation of a phase separation structure.
  • Alcohol solvents such as ethyl acetate and butyl acetate, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ether solvents such as diethyl ether and tetrahydrofuran, dimethylformamide, dimethylacetamide and dimethylimidazolidinone It is preferable that it is soluble in a general-purpose organic solvent such as an aprotic polar solvent such as dimethyl sulfoxide and N-methyl-2-pyrrolidone.
  • a general-purpose organic solvent such as an aprotic polar solvent such as dimethyl sulfoxide and N-methyl-2-pyrrolidone.
  • the particle diameter of the compound (B) having an azole ring in the solution is preferably 10 nm or less, more preferably 5 nm or less, and particularly preferably 2 nm or less. A solution in which particles having a particle diameter exceeding 2 nm are not confirmed can be most preferably used.
  • polyazole compounds and macrocyclic compounds generally have low solubility in a solvent.
  • the solubilization method is not particularly limited, but it is preferable to apply (1) spray drying method, (2) alkali dissolution, and (3) low molecular weight, (1) spray drying method, (2) alkali dissolution. Is more preferable, and (1) spray drying is more preferable.
  • the spray drying method of (1) is a method of instant drying by spraying a solution of a target substance as fine particles of several hundred ⁇ m or less in a flow of high-temperature air or nitrogen gas or in a vacuum chamber. It is. By applying this method, an amorphous porous body of the compound (B) having an azole ring can be obtained.
  • an insoluble / slightly soluble polyazole compound or a macrocyclic compound is stirred by stirring at room temperature. It can be easily dissolved.
  • the alkali dissolution of (2) is a method of forming a salt and solubilizing it by reacting the compound (B) having an azole ring with an alkali metal hydroxide.
  • a protic compound comprising a mixture of an organic solvent such as methanol, ethanol, 1-propanol, isopropyl alcohol, butanol or glycerin and water is used.
  • a polar solvent such as dimethyl sulfoxide or N-methyl-2-pyrrolidone.
  • the molecular weight used depends on the structure of the compound (B) having an azole ring.
  • the compound (B) having an azole ring For example, in the case of polybenzimidazole which is a kind of polyazole compound, Those having a weight average molecular weight of 1000 or more and 10,000 or less are preferably used.
  • a compound having a relatively low molecular weight By applying a compound having a relatively low molecular weight, the interaction between additive molecular chains can be reduced and solubilized.
  • the weight average molecular weight of the compound (B) having an azole ring used in the present invention is preferably 500 or more, more preferably 1000 or more.
  • the weight average molecular weight is less than 500, the compound (B) having an azole ring may bleed out on the surface of the polymer electrolyte composition, thereby reducing the power generation performance.
  • the weight average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less, and further preferably 300,000 or less.
  • the weight average molecular weight is larger than 1,000,000, the dispersibility of the compound (B) having an azole ring in the composition may deteriorate and processing may become difficult.
  • the compound (B) having an azole ring used in the polymer electrolyte composition of the present invention is preferably not dissolved in an aqueous solution containing a strongly acidic substance having a sulfonic acid group or the like.
  • the compound (B) having an azole ring preferably has a solubility in water and sulfuric acid at 60 ° C. of 100 mg / L or less, more preferably 20 mg / L or less, and particularly preferably 4 mg / L or less. If it is in this range, the compound (B) having an azole ring can maintain its effect without eluting out of the membrane, and more excellent chemical stability and durability can be obtained.
  • the content of the compound (B) having an azole ring used in the present invention can be appropriately selected in consideration of the balance between power generation characteristics and durability, and is not limited, but the polymer electrolyte composition 0.002 weight% or more of the whole is preferable, 0.01 weight% or more is more preferable, and 0.02 weight% or more is further more preferable.
  • the upper limit is preferably 15% by weight or less, more preferably 5% by weight or less, and further preferably 3% by weight or less. If it is less than 0.002% by weight, the durability may be insufficient. On the other hand, if it exceeds 15% by weight, proton conductivity may be insufficient.
  • the ionic group-containing polymer (A) and the compound (B) having an azole ring are compounds having an ionic group and an azole ring contained in the ionic group-containing polymer (A). What forms the intermolecular interaction in the part of the nitrogen atom contained in (B) is also preferable.
  • hydrogen peroxide and hydroxy radicals are highly hydrophilic compounds, and easily diffuse in the vicinity of an ionic group having high hydrophilicity and high water concentration in the electrolyte membrane.
  • intermolecular interaction examples include, but are not limited to, ion complexes, hydrogen bonds, dipole interactions, van der Waals forces, and the like. Among these, those that form ion complexes, hydrogen bonds, and dipole interactions are preferred, those that form ion complexes and hydrogen bonds are more preferred, and those that form ion complexes are particularly preferred.
  • the stronger the intermolecular interaction the stronger the cross-linking between the ionic group-containing polymer (A) and the compound (B) having an azole ring, which suppresses swelling / shrinkage of the polymer electrolyte composition.
  • the mechanical strength can be improved.
  • FT-IR Fourier-Transform Infrared Spectrometer
  • the compound (B) having an azole ring preferably does not contain an ionic group.
  • the ionic group refers to a carboxyl group, a sulfonic acid group, a phosphonic acid group, a hydroxyl group, and the like. If the compound (B) having an azole ring has an ionic group, the solubility in water and acid increases, so that the compound (B) having an azole ring is eluted out of the membrane and the chemical stability and durability are reduced. There is a case.
  • the ionic group contained in the compound (B) having an azole ring and the nitrogen atom of the azole ring cause a neutralization reaction, the intermolecular interaction with the ionic group contained in the ionic group-containing polymer (A) In some cases, the effects of decomposition of hydrogen peroxide and hydroxy radicals, suppression of swelling and shrinkage, and improvement of mechanical strength cannot be obtained sufficiently.
  • the method of blending the ionic ring-containing polymer (A) with the compound (B) having an azole ring is not particularly limited, and examples thereof include the following methods. Among these, it is more preferable to use the method (1) from the viewpoint of excellent mass productivity.
  • the contact method includes dipping, bar coating, spray coating, slit die, knife coating, air knife, brushing, gravure coating, screen printing, inkjet printing, doctor blade over roll (additive solution or dispersion liquid).
  • the method include, but are not limited to, a method in which the polymer electrolyte composition is applied to a molded body and then passed through a gap between a knife and a support roll to remove excess liquid.
  • Transition metal-containing additive (C) examples of the transition metal contained in the transition metal-containing additive (C) used in the present invention include cobalt, nickel, ruthenium, rhodium, palladium, silver, and gold. By using these metals, particularly excellent durability can be imparted to the polymer electrolyte composition. Of these, cobalt, nickel, ruthenium, and rhodium are preferably used because durability can be further improved, and cobalt, nickel, and ruthenium are particularly preferably used because they can be used at low cost.
  • the embodiment of the transition metal-containing additive (C) used in the present invention is not particularly limited, but specific examples include zero-valent metals, oxides, fluorides, chlorides, bromides, iodides, and nitrates. , Sulfate, sulfonate, carbonate, phosphate, phosphonate, acetate, oxalate, acetylacetonate complex, phenanthroline complex, and the like. Above all, it is highly effective in suppressing oxidative degradation, so it is zero-valent metal, oxide, chloride, bromide, iodide, nitrate, sulfate, sulfonate, carbonate, phosphate, phosphonate, acetic acid.
  • Salts, acetylacetonato complexes, and phenanthroline complexes are preferable, and zero-valent metals, oxides, sulfates, nitrates, phosphates, phosphonates, acetylacetonato complexes, and phenanthroline complexes are more preferable because of high elution resistance. Further, zero-valent metals, oxides, nitrates, acetylacetonato complexes, and phenanthroline complexes are more preferable because they are inexpensive and easy to add to the electrolyte composition.
  • the content of the transition metal-containing additive (C) to be used can be appropriately selected in consideration of the balance between power generation characteristics and durability, and is not limited, but is not limited to 0. 0% of the entire polymer electrolyte composition. 002% by weight or more is preferable, 0.01% by weight or more is more preferable, and 0.02% by weight or more is more preferable. On the other hand, the upper limit is preferably 15% by weight or less, more preferably 5% by weight or less, and further preferably 3% by weight or less. If it is less than 0.002% by weight, the durability may be insufficient. On the other hand, if it exceeds 15% by weight, proton conductivity may be insufficient.
  • the content ratio of the compound (B) having an azole ring and the transition metal-containing additive (C) used in the present invention can be appropriately selected in consideration of the balance between power generation characteristics and durability, and is limited.
  • the molar ratio of nitrogen / transition metal is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 1 or more.
  • the upper limit is preferably 100 or less, more preferably 20 or less, and even more preferably 10 or less. When it is less than 0.01, proton conductivity and hot water resistance may be insufficient. On the other hand, if it exceeds 100, the durability improving effect may be reduced.
  • the location where the transition metal-containing additive (C) is contained is not particularly limited in the catalyst layer-coated electrolyte membrane and membrane electrode assembly described below, but specifically, the electrolyte membrane, cathode catalyst layer, anode catalyst layer, cathode Between the catalyst layer and the first surface of the polymer electrolyte membrane, between the anode catalyst layer and the second surface of the polymer electrolyte membrane, the cathode gas diffusion layer, between the cathode gas diffusion layer and the cathode catalyst layer, and anode gas diffusion A layer, an anode gas diffusion layer, and an anode catalyst layer.
  • the cathode catalyst layer, the cathode catalyst layer and the second surface of the polymer electrolyte membrane between the cathode gas diffusion layer and the cathode catalyst layer can be obtained by suppressing the deterioration of the catalyst layer due to the reverse current. Is preferred.
  • the method of blending the transition metal-containing additive (C) into the catalyst layer-covered electrolyte membrane or membrane electrode assembly described below is not particularly limited, and is appropriately selected according to the type of the transition metal-containing additive (C) and the place where it is added. For example, the following methods can be mentioned. (1) After dissolving or dispersing the transition metal-containing additive (C) in a solution or dispersion of the ionic group-containing polymer (A), a film is formed using the obtained liquid, and a polymer electrolyte membrane is obtained. How to make. (2) A method in which the polymer electrolyte membrane, the catalyst layer, and the gas diffusion layer are brought into contact with the liquid in which the transition metal-containing additive (C) is dissolved. (3) A method in which the transition metal-containing additive (C) is blended in the catalyst ink or decal sheet.
  • Examples of the contact method include dipping, bar coating, spray coating, slit die, knife coating, air knife, brushing, gravure coating, screen printing, ink jet printing, doctor blade overroll (additive solution or dispersion as a polymer electrolyte composition)
  • a method of applying to a molded article and then removing excess liquid through a gap between the knife and the support roll) is not limited thereto.
  • Nitrogen atoms and transition metal atoms and / or ions contained in the compound (B) having an azole ring function as a complex that decomposes peroxides and hydroxy radicals by forming a complex, and Suppressing elution.
  • the polymer electrolyte composition of the present invention is particularly suitably used as a polymer electrolyte molded body.
  • the polymer electrolyte molded body means a molded body containing the polymer electrolyte composition of the present invention.
  • the polymer electrolyte molded body of the present invention includes membranes (including films and films), plates, fibers, hollow fibers, particles, lumps, micropores, coatings, and foams. It can take various forms depending on the intended use.
  • the polymer can be applied to a wide range of applications because it can improve the design freedom of the polymer and improve various properties such as mechanical properties and solvent resistance.
  • the polymer electrolyte molded body is preferably a membrane.
  • the polymer electrolyte molded body of the present invention preferably has a co-continuous or lamellar phase separation structure.
  • a phase-separated structure includes, for example, an ionic group-containing polymer (A) having two or more incompatible segments such as a segment containing an ionic group and a segment not containing an ionic group as described later.
  • A ionic group-containing polymer
  • the structural form can be roughly divided into four types: co-continuous (M1), lamella (M2), cylinder (M3), and sea island (M4). 1).
  • the phase separation structure is composed of a hydrophilic domain composed of a component containing an ionic group and a component not containing an ionic group. Are often formed from hydrophobic domains.
  • the white continuous phase is formed by one domain selected from the hydrophilic domain and the hydrophobic domain, and the dark continuous phase or dispersed phase is formed by the other domain.
  • both the hydrophilic domain and the hydrophobic domain form a continuous phase.
  • the compound (B) having an azole ring and the transition metal-containing additive (C) are polar (hydrophilic). And (hydrophobic) are appropriately selected to concentrate on the hydrophilic domain formed by the segment (A1) containing an ionic group or the hydrophobic domain formed by the segment (A2) containing no ionic group. It is possible to arrange.
  • Hydroxyl radical and hydrogen peroxide are usually highly hydrophilic and are present in the hydrophilic domain formed by the segment (A1) containing an ionic group and are considered to cut the segment. Therefore, the compound (B) having a hydrophilic azole ring and the transition metal-containing additive (C) are effective for stabilizing the segment (A1) containing an ionic group. From this point of view, the compound (B) having the azole ring present in the hydrophilic domain and the concentration of the transition metal-containing additive (C) having the azole ring existing in the hydrophobic domain (B ) And the concentration of the transition metal-containing additive (C) are each preferably twice or more.
  • the concentration of the compound (B) having an azole ring and the transition metal-containing additive (C) in each domain is determined by an energy dispersive X-ray analysis (EDX) or electron beam microanalyzer (EPMA) to determine the content of nitrogen and transition metals by mapping.
  • EDX energy dispersive X-ray analysis
  • EPMA electron beam microanalyzer
  • elemental analysis is performed at 50 points for each of the hydrophilic domain and the hydrophobic domain to determine the average amount of nitrogen and average amount of transition metal in the domain, and the concentration of the compound (B) having an azole ring is as follows.
  • the concentration in each domain can be calculated according to the following formula.
  • Concentration (% by weight) of compound (B) having an azole ring 100 ⁇ [average nitrogen content in domain (% by weight) ⁇ polymer nitrogen content (% by weight)] / [Nitrogen content (% by weight) of compound (B) having an azole ring-polymer nitrogen content (% by weight)]
  • the amount of polymer nitrogen and the amount of nitrogen in the compound (B) having an azole ring are the amounts of nitrogen contained in the polymer electrolyte and the compound (B) having an azole ring, respectively.
  • the hydrophobic domain formed by the segment (A2) not containing an ionic group is a component responsible for mechanical strength
  • physical durability can be obtained by arranging the compound (B) having a hydrophobic azole ring. It is thought that there is an effect of improving.
  • the compound (B) having a hydrophilic azole ring and the compound (B) having a hydrophobic azole ring are also preferably used in combination as necessary.
  • phase separation structure is described in, for example, Annual Review of Physical Chemistry, 41, 1990, p. 525 etc.
  • excellent proton conductivity can be realized even under low humidification and low temperature conditions.
  • a polymer electrolyte excellent in proton conductivity is formed by forming a continuous proton conducting channel.
  • a molded body can be obtained, but at the same time, a polymer electrolyte molded body having excellent fuel barrier properties, solvent resistance, mechanical strength, and physical durability due to the crystallinity of the hydrophobic domain can be realized.
  • a co-continuous (M1) phase separation structure is particularly preferred.
  • the domain means a lump formed by aggregating similar substances and segments in one molded body.
  • having a co-continuous (M1) or lamellar (M2) phase separation structure can be confirmed by observing a desired image by the following method.
  • a three-dimensional view of a digital slice taken from three directions of length, width, and height is compared with a three-dimensional view obtained by TEM tomography observation of a polymer electrolyte molded body.
  • the phase separation structure is
  • the hydrophilic domain containing (A1) and the hydrophobic domain containing (A2) together form a continuous phase in all three views.
  • each of the continuous phases shows a complicated pattern, whereas in the case of a lamellar structure, a pattern in which the layers are continuous is shown.
  • the continuous phase means a phase in which individual domains are connected without being isolated from each other macroscopically, but there may be a part that is not partially connected.
  • a polymer in order to clarify the aggregation state and contrast of the segment (A1) containing an ionic group and the segment (A2) containing no ionic group, a polymer is added in a 2% by weight lead acetate aqueous solution.
  • the ionic group is ion-exchanged with lead, and then subjected to observation with a transmission electron microscope (TEM) and TEM tomography.
  • TEM transmission electron microscope
  • a phase separation structure is observed when TEM observation is performed at a magnification of 50,000 times, and an average interlayer distance or an average interparticle distance measured by image processing is 5 nm or more.
  • the upper limit is preferably 500 nm or less, more preferably 50 nm or less, and even more preferably 30 nm or less.
  • the block copolymer used as the ionic group-containing polymer (A) preferably has crystallinity while having a phase separation structure, and crystallinity is recognized by differential scanning calorimetry (DSC) or wide-angle X-ray diffraction. Is preferred. Specifically, it is preferable that the amount of crystallization measured by differential scanning calorimetry is 0.1 J / g or more, or the degree of crystallinity measured by wide-angle X-ray diffraction is 0.5% or more. Note that “having crystallinity” means that the polymer can be crystallized when the temperature is raised, has a crystallizable property, or has already been crystallized.
  • An amorphous polymer means a polymer that is not a crystalline polymer and that does not substantially proceed with crystallization. Therefore, even if it is a crystalline polymer, when the crystallization has not progressed sufficiently, the polymer may be in an amorphous state.
  • the film thickness of the polymer electrolyte membrane of the present invention is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and even more preferably 10 ⁇ m or more from the viewpoint of mechanical strength and physical durability of the membrane that can withstand practical use. In order to reduce membrane resistance, that is, improve power generation performance, it is preferably 2000 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 30 ⁇ m or less.
  • the film thickness can be controlled by the solution concentration or the coating thickness on the substrate.
  • the polymer electrolyte membrane of the present invention has various polymers, elastomers, fillers, and the like for the purpose of improving mechanical strength, thermal stability, workability, etc. within the range that does not adversely affect the above-mentioned various properties.
  • Additives such as fine particles, crystallization nucleating agents, plasticizers, stabilizers, antioxidants or mold release agents used in ordinary polymer compounds may be included.
  • you may reinforce with a microporous film, a nonwoven fabric, a mesh, etc.
  • the catalyst layer-coated electrolyte membrane of the present invention includes a polymer electrolyte membrane containing an ionic group-containing polymer (A) described later, an anode catalyst layer formed on the first surface of the polymer electrolyte membrane, and the polymer electrolyte.
  • a catalyst layer-coated electrolyte membrane comprising at least one transition metal-containing additive (C) selected from the group consisting of cobalt, nickel, ruthenium, rhodium, palladium, silver and gold.
  • the trivalent nitrogen atom contained in the compound (B) having an azole ring is oxidized to a pentavalent N-oxide to function as a peroxide decomposing agent.
  • the nitrogen atom contained in the compound (B) having an azole ring that has reacted with a peroxide and oxidized to a pentavalent N-oxide is reduced with hydrogen by the catalytic action of the transition metal-containing additive (C). And regenerate as trivalent nitrogen.
  • transition metal itself reacts with peroxides and hydroxy radicals to render them harmless.
  • a nitrogen atom contained in the compound (B) having an azole ring and a transition metal atom and / or an ion contained in the transition metal-containing additive (C) form a complex to form a peroxide or a hydroxy radical. It functions as a complex that decomposes and suppresses the elution of transition metals.
  • the membrane electrode assembly of the present invention includes a polymer electrolyte membrane containing an ionic group-containing polymer (A) described later, an anode catalyst layer formed on the first surface of the polymer electrolyte membrane, and the polymer electrolyte membrane.
  • a membrane electrode assembly having a cathode catalyst layer, an anode gas diffusion layer, and a cathode gas diffusion layer formed on the second surface of the membrane, wherein at least one selected from a polymer electrolyte membrane, an anode catalyst layer, and a cathode catalyst layer
  • Bonding method of polymer electrolyte membrane and electrode (anode catalyst layer, cathode catalyst layer, anode gas diffusion layer and cathode gas diffusion layer) when using the polymer electrolyte membrane of the present invention as a fuel cell (manufacturing method of membrane electrode assembly) )
  • Is not particularly limited, and known methods for example, chemical plating method described in Electrochemistry, 1985, 53, p.269, edited by Electrochemical Society (J. Electrochem. Soc.), Electrochemical Science and Technology ( Electrochemical Science and Technology), 1988, 135, 9, p.2209, etc., can be applied.
  • a catalyst ink made of catalyst-carrying carbon or an ionic conductor is applied to a polymer electrolyte membrane, or a decal sheet obtained by applying the catalyst ink to a substrate and drying to form a sheet is heated and polymerized.
  • a method of further bonding a gas diffusion electrode to the catalyst layer-covered electrolyte membrane produced by the method of transferring to the electrolyte membrane is also applicable.
  • the temperature and pressure may be appropriately selected depending on the thickness of the electrolyte membrane, the moisture content, the catalyst layer, and the electrode substrate. Further, in the present invention, it is possible to form a composite by pressing even when the electrolyte membrane is in a dry state or in a state of absorbing water.
  • Specific pressing methods include a roll press that defines pressure and clearance, and a flat plate press that defines pressure. From the viewpoint of industrial productivity and suppression of thermal decomposition of a polymer material having an ionic group, it is 0. It is preferably carried out in the range of from °C to 250 °C.
  • the pressurization is preferably as weak as possible from the viewpoint of electrolyte membrane and electrode protection.
  • a pressure of 10 MPa or less is preferable, and the electrode and the electrolyte membrane are stacked without carrying out the complexing by the hot press process.
  • Cell formation is also one of the preferred options from the viewpoint of preventing short-circuiting of the anode and cathode electrodes.
  • this method when power generation is repeated as a fuel cell, the deterioration of the electrolyte membrane presumed to be caused by a short-circuited portion tends to be suppressed, and the durability as a fuel cell is improved.
  • the location where the compound (B) having an azole ring is contained is not particularly limited, but at least one location selected from an electrolyte membrane, a cathode catalyst layer, and an anode catalyst layer. included.
  • the location where the transition metal-containing additive (C) is contained is not particularly limited, but the electrolyte membrane, the cathode catalyst layer, the anode catalyst layer, the cathode catalyst layer, and the polymer Between the first surface of the electrolyte membrane, between the anode catalyst layer and the second surface of the polymer electrolyte membrane, cathode gas diffusion layer, between the cathode gas diffusion layer and the cathode catalyst layer, anode gas diffusion layer, anode gas diffusion It is contained in at least one location selected between the layer and the anode catalyst layer.
  • the electrolyte membrane, anode catalyst layer, cathode catalyst layer It is preferably any of them, and more preferably contained in the polymer electrolyte membrane from the viewpoint of suppressing a decrease in molecular weight due to chemical deterioration and membrane breakage due to swelling shrinkage.
  • the polymer electrolyte composition, polymer electrolyte membrane, catalyst layer-covered electrolyte membrane, and membrane electrode assembly of the present invention preferably further contain an additive containing a phosphorus atom.
  • the form in which the phosphorus atom is contained in the additive is not particularly limited, but is preferably a trivalent organic phosphorus compound because of its high ability to decompose hydrogen peroxide and hydroxy radicals, In order to suppress elution in the interior, phosphine and phosphinite compounds are more preferable.
  • the content of the phosphorus-containing additive used in the present invention can be appropriately selected in consideration of the balance between power generation characteristics and durability, and is not limited. 002% by weight or more is preferable, 0.01% by weight or more is more preferable, and 0.02% by weight or more is more preferable. About an upper limit, 15 weight% or less is preferable, 5 weight% or less is more preferable, and 3 weight% or less is further more preferable. If it is less than 0.002% by weight, the durability may be insufficient. On the other hand, if it exceeds 15% by weight, proton conductivity may be insufficient.
  • the polymer electrolyte composition, polymer electrolyte membrane, catalyst layer-covered electrolyte membrane, and membrane electrode assembly of the present invention is at least one selected from cerium, manganese, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, and iridium. It is also preferred to further contain other transition metals of the species. These other transition metals can be used in one or more embodiments selected from the group consisting of metals themselves, metal ions, salts containing metal ions, complexes containing metal ions, and metal oxides.
  • cerium, manganese, vanadium, molybdenum, tungsten, iridium are preferably used because of their high functions as radical scavengers and peroxide decomposers, more preferably cerium, manganese, iridium, and still more preferably.
  • Cerium, manganese and iridium particularly preferably cerium and manganese.
  • the content of other transition metals used in the present invention can be appropriately selected in consideration of the balance between power generation characteristics and durability, and is not limited. 002% by weight or more is preferable, 0.01% by weight or more is more preferable, and 0.02% by weight or more is more preferable.
  • the upper limit is preferably 15% by weight or less, more preferably 5% by weight or less, and further preferably 3% by weight or less. If it is less than 0.002% by weight, durability may be insufficient. On the other hand, if it exceeds 15% by weight, proton conductivity may be insufficient.
  • the content ratio of the compound (B) having an azole ring and other transition metals used in the present invention can be appropriately selected in consideration of the balance between power generation characteristics and durability, and is not limited.
  • the molar ratio of nitrogen / other transition metal is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 1 or more.
  • the upper limit is preferably 100 or less, more preferably 20 or less, and still more preferably 10 or less. If it is less than 0.01, proton conductivity and hot water resistance may be insufficient. On the other hand, if it exceeds 100, the durability improving effect may be reduced.
  • transition metal ions are not particularly limited, but specific examples include chloride ions, bromide ions, iodide ions, nitrates, sulfates, sulfonates, carbonates, phosphates, Examples thereof include phosphonates, acetates, oxalates, and acetylacetonate complexes.
  • nitrates, sulfates, sulfonates, carbonates, phosphates, phosphonates, and acetates are preferable because they are highly effective in suppressing oxidative degradation, and are inexpensive and easy to add to the electrolyte composition. Therefore, nitrates, phosphates, and acetates are more preferable.
  • transition metal oxides include cerium oxide, manganese oxide, chromium oxide, and iridium oxide. Of these, cerium oxide and manganese oxide are preferably used because they have a high effect of suppressing oxidative degradation.
  • the polymer electrolyte composition of the present invention preferably further contains a sulfur-containing additive.
  • a sulfur-containing additive sulfides are preferable from the viewpoint of power generation performance, aromatic polysulfides are more preferable from the viewpoint of heat resistance and chemical stability, and polyparaphenylene sulfide is particularly preferable from the viewpoint of manufacturing cost.
  • the ionic group-containing polymer (A) used in the present invention is not limited in structure as long as it contains an ionic group as described later and can achieve both power generation characteristics and chemical stability. Fluoropolymers and hydrocarbon polymers are typical examples.
  • the perfluoro polymer is a polymer in which most or all of the hydrogens of the alkyl group and / or alkylene group in the polymer are substituted with fluorine atoms.
  • a perfluoro polymer having an ionic group Commercial products such as Nafion (registered trademark) (manufactured by DuPont), Flemion (registered trademark) (manufactured by Asahi Glass) and Aciplex (registered trademark) (manufactured by Asahi Kasei) can be mentioned.
  • These perfluoro polymers can be preferably used because the swelling and shrinkage accompanying the change in humidity are small, and the electrolyte membrane is not easily damaged by the change in humidity.
  • hydrocarbon polymer As the ionic group-containing polymer electrolyte.
  • the hydrocarbon polymer can be preferably used from the viewpoint of mechanical strength, physical durability, chemical stability, and the like, and is more preferably a hydrocarbon polymer having an aromatic ring in the main chain.
  • polymers having sufficient mechanical strength and physical durability that are used as engineering plastics are preferable.
  • the aromatic ring may include not only an aromatic ring consisting only of hydrocarbons but also a hetero ring. Further, a part of the aliphatic units may constitute a polymer together with the aromatic ring unit.
  • hydrocarbon polymer having an aromatic ring in the main chain examples include polysulfone, polyethersulfone, polyphenylene oxide, polyarylene ether polymer, polyphenylene sulfide, polyphenylene sulfide sulfone, polyparaphenylene, polyarylene polymer, polyarylene.
  • examples include ketones, polyether ketones, polyarylene phosphine oxides, polyether phosphine oxides, polybenzoxazoles, polybenzthiazoles, polybenzimidazoles, aromatic polyamides, polyimides, polyether imides, polyimide sulfones, and the like. It is not limited to these.
  • aromatic polyether polymer In view of mechanical strength, physical durability, and manufacturing cost, an aromatic polyether polymer is preferable. In addition, it exhibits crystallinity due to good packing of the main chain skeleton structure and extremely strong intermolecular cohesion, and has the property of not dissolving in general solvents, and is excellent in tensile strength and elongation, tear strength and fatigue resistance. Aromatic polyether ketone polymers are particularly preferred.
  • the aromatic polyether ketone polymer is a general term for polymers having at least an aromatic ring, an ether bond and a ketone bond in the main chain, and includes an aromatic polyether ketone, an aromatic polyether ketone ketone, an aromatic Aromatic polyether ether ketone, aromatic polyether ether ketone ketone, aromatic polyether ketone ether ketone ketone, aromatic polyether ketone sulfone, aromatic polyether ketone phosphine oxide, aromatic polyether ketone nitrile and the like.
  • the ionic group of the ionic group-containing polymer (A) is preferably a negatively charged atomic group, and preferably has proton exchange ability.
  • a functional group a sulfonic acid group, a sulfonimide group, a sulfuric acid group, a phosphonic acid group, a phosphoric acid group, and a carboxylic acid group are preferably used.
  • the ionic group includes a case where it is a salt.
  • the counter cation in the case where the ionic group forms a salt include an arbitrary metal cation, NR 4 + (R is an arbitrary organic group), and the like.
  • R is an arbitrary organic group
  • the valence and the like are not particularly limited and can be used.
  • preferable metal cations include cations such as Li, Na, K, Rh, Mg, Ca, Sr, Ti, Al, Fe, Pt, Rh, Ru, Ir, and Pd. Among them, Na, K, and Li cations that are inexpensive and can be easily proton-substituted are preferably used.
  • a method for introducing an ionic group into the structure includes a method of polymerizing using a monomer having an ionic group, The method of introduce
  • a monomer having an ionic group in a repeating unit may be used as a method for polymerizing using a monomer having an ionic group. Such a method is described, for example, in Journal of Membrane Science, 197, 2002, p. 231-242. This method is preferable because it is easy to control the ion exchange capacity of the polymer (hereinafter sometimes abbreviated as IEC).
  • a method for introducing an ionic group by a polymer reaction for example, Polymer Preprints (Japan), 51, 2002, p. It is possible by the method described in 750 etc.
  • Introduction of a phosphate group into an aromatic polymer can be achieved by, for example, phosphoric esterification of an aromatic polymer having a hydroxyl group.
  • Carboxylic acid groups can be introduced into the aromatic polymer by, for example, oxidizing an aromatic polymer having an alkyl group or a hydroxyalkyl group.
  • the introduction of a sulfate group into an aromatic polymer can be achieved by, for example, sulfate esterification of an aromatic polymer having a hydroxyl group.
  • the method described in JP-A-2-16126 or JP-A-2-208322 can be used.
  • sulfonation by reacting an aromatic polymer with a sulfonating agent such as chlorosulfonic acid in a solvent such as chloroform or by reacting in concentrated sulfuric acid or fuming sulfuric acid.
  • a sulfonating agent such as chlorosulfonic acid in a solvent such as chloroform
  • the sulfonating agent is not particularly limited as long as it sulfonates an aromatic polymer, and sulfur trioxide or the like can be used in addition to the above.
  • the degree of sulfonation can be controlled by the amount of sulfonating agent used, the reaction temperature and the reaction time.
  • Introduction of a sulfonimide group into an aromatic polymer can be achieved, for example, by a method of reacting a sulfonic acid group and a sulfonamide group.
  • the molecular weight of the ionic group-containing polymer (A) thus obtained is preferably a weight average molecular weight in terms of polystyrene of at least 10,000 and more preferably at least 10,000. About an upper limit, 5 million or less are preferable and 500,000 or less are more preferable. If it is less than 10,000, any of mechanical strength, physical durability, and solvent resistance may be insufficient, such as cracks formed in the molded film. On the other hand, if it exceeds 5,000,000, the solubility may be insufficient, the solution viscosity may be high, and the processability may be poor.
  • the ionic group-containing polymer (A) used in the present invention includes a segment (A1) containing an ionic group and a segment containing no ionic group from the viewpoint of proton conductivity and power generation characteristics under low humidification conditions. It is more preferable that the block copolymer contains at least one (A2). Further, a block copolymer having a linker site for connecting the segments is more preferable. Due to the presence of the linker, different segments can be linked while effectively suppressing side reactions.
  • the number average molecular weight of the segment (A1) containing an ionic group and the segment (A2) containing no ionic group is related to the domain size of the phase separation structure, and the proton conductivity and physical durability at low humidification From the balance, it is more preferably 50,000 or more, more preferably 10,000 or more, and most preferably 15,000 or more. Moreover, 50,000 or less is more preferable, More preferably, it is 40,000 or less, Most preferably, it is 30,000 or less.
  • the segment (A1) containing an ionic group is represented by the following general formula (S1)
  • the segment (A2) containing no ionic group is represented by the following general formula What contains the structural unit represented by Formula (S2) is preferable.
  • Ar 1 to Ar 4 represent any divalent arylene group, and at least one of Ar 1 and Ar 2 has an ionic group as a substituent.
  • Ar 3 and Ar 4 is .
  • Ar 1 ⁇ Ar 4 may be optionally substituted with also a good .
  • Ar 1 ⁇ Ar 4 is a non-ionic group group not having have an ionic group as a substituent structural units Each may be the same or different. * Represents a binding site with the general formula (S1) or other structural unit.)
  • Ar 5 to Ar 8 represent any divalent arylene group, which may be substituted, but does not have an ionic group. Ar 5 to Ar 8 are the same for each structural unit. However, it may be different. * Represents a binding site with the general formula (S2) or other structural unit.)
  • the block copolymer containing the structural units represented by the above general formulas (S1) and (S2) all arylene groups are chemically stabilized with an electron-attracting ketone group, and the surface is close to a plane. Due to the structure, the packing of the molecule is improved, so that it is toughened by imparting crystallinity, softened by lowering the glass transition temperature, and the physical durability is increased.
  • Examples of the unsubstituted skeleton of the divalent arylene groups Ar 1 to Ar 8 in the general formulas (S1) and (S2) include hydrocarbon-based arylene groups such as a phenylene group, a naphthylene group, a biphenylene group, and a fluorenediyl group, Heteroarylene groups such as pyridinediyl, quinoxalinediyl, thiophenediyl and the like can be mentioned, preferably a phenylene group, more preferably a p-phenylene group.
  • the segment (A1) containing an ionic group is more preferably a structural unit that is chemically stable, has an increased acidity due to an electron withdrawing effect, and is introduced with an ionic group at a high density.
  • the segment (A2) not containing an ionic group is more preferably a structural unit that is chemically stable and exhibits crystallinity due to strong intermolecular cohesion.
  • a content rate of the structural unit represented by general formula (S1) contained in the segment (A1) containing the said ionic group 20 mol% or more in the segment (A1) containing an ionic group is preferable. 50 mol% or more is more preferable, and 80 mol% or more is more preferable.
  • content rate of the structural unit represented by general formula (S2) contained in the segment (A2) which does not contain an ionic group 20 mol% or more in the segment (A2) which does not contain an ionic group is Preferably, 50 mol% or more is more preferable, and 80 mol% or more is more preferable.
  • the present invention for mechanical strength, dimensional stability and physical durability due to crystallinity May be insufficient.
  • Preferred examples of the structural unit represented by the general formula (S1) include structural units represented by the following general formula (P2) in terms of raw material availability.
  • a structural unit represented by the following formula (P3) is more preferable, and a structural unit represented by the following formula (P4) is more preferable.
  • M 1 ⁇ M 4 represents a hydrogen cation, a metal cation, an ammonium cation NR 4 + (R represents any organic group), identical to each other is M 1 ⁇ M 4 R1 to r4 each independently represents an integer of 0 to 4, r1 + r2 represents an integer of 1 to 8, and r1 to r4 may be different for each structural unit.
  • * Represents a binding site with the formula (P2) (P3) (P4) or other structural unit.
  • the block in the case of using a block copolymer containing at least one segment (A1) containing an ionic group and one or more segments (A2) containing no ionic group as the ionic group-containing polymer (A) in the present invention.
  • the molar composition ratio (A1 / A2) of the segment (A1) containing an ionic group and the segment (A2) containing no ionic group is more preferably 0.2 or more. 33 or more is more preferable, and 0.5 or more is more preferable. Moreover, 5 or less is preferable, 3 or less is more preferable, and 2 or less is further more preferable.
  • the molar composition ratio A1 / A2 is less than 0.2 or exceeds 5, proton conductivity under low humidification conditions may be insufficient, or hot water resistance and physical durability may be insufficient.
  • the ion exchange capacity of the segment (A1) containing an ionic group is preferably 2.5 meq / g or more, more preferably 3 meq / g or more, from the viewpoint of proton conductivity under low humidification conditions, and 3.5 meq / g. g or more is more preferable. Moreover, 6.5 meq / g or less is preferable, 5 meq / g or less is more preferable, and 4.5 meq / g or less is further more preferable.
  • the ion exchange capacity of the segment (A2) not containing an ionic group is preferably 1 meq / g or less, more preferably 0.5 meq / g or less, from the viewpoint of hot water resistance, mechanical strength, dimensional stability, and physical durability. 0.1 meq / g or less is more preferable. When the ion exchange capacity of the segment (A2) not containing an ionic group exceeds 1 meq / g, the hot water resistance, mechanical strength, dimensional stability, and physical durability may be insufficient.
  • the ionic group-containing polymer (A) a block copolymer containing at least one segment (A1) containing an ionic group and one or more segments (A2) containing no ionic group is used.
  • the ion exchange capacity is preferably 0.1 to 5 meq / g, more preferably 1.5 meq / g or more, and further preferably 2 meq / g or more from the viewpoint of the balance between proton conductivity and water resistance. preferable. Moreover, 3.5 meq / g or less is more preferable, and 3 meq / g or less is further more preferable.
  • the ion exchange capacity is less than 0.1 meq / g, proton conductivity may be insufficient, and when it is greater than 5 meq / g, water resistance may be insufficient.
  • the ion exchange capacity is a value determined by a neutralization titration method.
  • the neutralization titration method is performed as follows. In addition, a measurement shall be performed 3 times or more and the average value shall be taken.
  • (2) Add 50 mL of 5% by weight aqueous sodium sulfate solution to the electrolyte, and leave it for 12 hours for ion exchange.
  • the generated sulfuric acid is titrated using 0.01 mol / L sodium hydroxide aqueous solution.
  • a commercially available phenolphthalein solution for titration (0.1 w / v%) is added as an indicator, and the point at which light reddish purple is obtained is taken as the end point.
  • the ion exchange capacity is determined by
  • Ion exchange capacity (meq / g) [Concentration of sodium hydroxide aqueous solution (mmol / ml) ⁇ Drip amount (ml)] / Dry weight of sample (g)
  • the method for synthesizing the segment (A1) containing an ionic group and the segment (A2) not containing an ionic group is not particularly limited as long as a substantially sufficient molecular weight can be obtained. It can be synthesized using an aromatic nucleophilic substitution reaction of an aromatic group active dihalide compound and a divalent phenol compound, or an aromatic nucleophilic substitution reaction of a halogenated aromatic phenol compound.
  • the aromatic active dihalide compound used for the synthesis of the segment (A1) containing an ionic group the use of a compound in which an ionic group is introduced into the aromatic active dihalide compound as a monomer, chemical stability, production cost, ion
  • the amount of the sex group is preferable from the viewpoint that precise control is possible.
  • Preferred examples of the monomer having a sulfonic acid group as an ionic group include 3,3′-disulfonate-4,4′-dichlorodiphenylsulfone and 3,3′-disulfonate-4,4′-difluorodiphenylsulfone.
  • 3,3′-disulfonate-4,4′-dichlorodiphenyl ketone and 3,3′-disulfonate-4,4′-difluorodiphenyl ketone are more preferable from the viewpoint of chemical stability and physical durability. From the viewpoint of polymerization activity, 3,3′-disulfonate-4,4′-difluorodiphenyl ketone is most preferable.
  • Examples of the aromatic active dihalide compound having no ionic group used for the synthesis of the segment (A1) containing an ionic group and the segment (A2) containing no ionic group include 4,4′-dichlorodiphenylsulfone, 4,4′-difluorodiphenylsulfone, 4,4′-dichlorodiphenyl ketone, 4,4′-difluorodiphenyl ketone, 4,4′-dichlorodiphenylphenylphosphine oxide, 4,4′-difluorodiphenylphenylphosphine oxide, 2 , 6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, and the like.
  • 4,4′-dichlorodiphenyl ketone and 4,4′-difluorodiphenyl ketone are more preferable in terms of imparting crystallinity, mechanical strength, physical durability, and hot water resistance, and 4,4′- in terms of polymerization activity.
  • Difluorodiphenyl ketone is most preferred.
  • aromatic active dihalide compounds can be used alone, but a plurality of aromatic active dihalide compounds can also be used in combination.
  • a halogenated aromatic hydroxy compound can be mentioned as a monomer having no ionic group used for the synthesis of the segment (A1) containing an ionic group and the segment (A2) containing no ionic group.
  • the said segment can synthesize
  • the halogenated aromatic hydroxy compound is not particularly limited, but 4-hydroxy-4′-chlorobenzophenone, 4-hydroxy-4′-fluorobenzophenone, 4-hydroxy-4′-chlorodiphenylsulfone, 4-hydroxy -4′-fluorodiphenylsulfone, 4- (4′-hydroxybiphenyl) (4-chlorophenyl) sulfone, 4- (4′-hydroxybiphenyl) (4-fluorophenyl) sulfone, 4- (4′-hydroxybiphenyl) Examples include (4-chlorophenyl) ketone, 4- (4′-hydroxybiphenyl) (4-fluorophenyl) ketone, and the like.
  • these halogenated aromatic hydroxy compounds may be reacted together to synthesize an aromatic polyether compound.
  • the method for synthesizing the block copolymer is not particularly limited as long as a substantially sufficient molecular weight is obtained.
  • the segment containing an ionic group and the segment containing no ionic group are aromatic. It can be synthesized using a nucleophilic substitution reaction.
  • the monomer mixture or segment mixture is reacted in the presence of a basic compound.
  • a basic compound such polymerization can be carried out in a temperature range of 0 to 350 ° C., but a temperature of 50 to 250 ° C. is preferable. When the temperature is lower than 0 ° C, the reaction tends not to proceed sufficiently. When the temperature is higher than 350 ° C, the polymer may be decomposed.
  • the polymerization reaction can be carried out in the absence of a solvent, but is preferably carried out in a solvent.
  • Solvents that can be used include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphontriamide, etc.
  • Examples of the aprotic polar organic solvent include, but are not limited to, any solvents that can be used as a stable solvent in the aromatic nucleophilic substitution reaction. These organic solvents may be used alone or as a mixture of two or more.
  • Examples of the basic compound used for the aromatic nucleophilic substitution reaction include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc., but aromatic diols are active phenoxide structures. However, the present invention is not limited to these and can be used. In order to increase the nucleophilicity of phenoxide, it is also preferable to add a crown ether such as 18-crown-6. These crown ethers may be preferably used because they may be coordinated to a sodium ion or potassium ion of a sulfonic acid group to improve the solubility in an organic solvent.
  • water may be generated as a by-product.
  • water can be removed from the system as an azeotrope by coexisting toluene or the like in the reaction system.
  • a water-absorbing agent such as molecular sieve can also be used.
  • Azeotropic agents used to remove reaction water or water introduced during the reaction generally do not substantially interfere with polymerization, co-distill with water and boil between about 25 ° C. and about 250 ° C. Any inert compound.
  • Commonly used azeotropic agents include benzene, toluene, xylene, chlorobenzene, methylene chloride, dichlorobenzene, trichlorobenzene, cyclohexane and the like. Of course, it is beneficial to select an azeotropic agent whose boiling point is lower than that of the dipolar solvent used.
  • Azeotropic agents are often used, but it is not always necessary when high reaction temperatures are used, for example, temperatures above 200 ° C., especially when the inert gas is continuously sparged into the reaction mixture. In general, it is desirable to carry out the reaction in an inert atmosphere and in the absence of oxygen.
  • the aromatic nucleophilic substitution reaction is carried out in a solvent
  • the desired polymer is obtained by removing the solvent from the reaction solution by evaporation and washing the residue as necessary.
  • the reaction solution by adding the reaction solution to a solvent having low polymer solubility and high by-product inorganic salt solubility, the inorganic salt is removed, the polymer is precipitated as a solid, and the polymer is obtained by filtering the precipitate. You can also.
  • the recovered polymer is optionally washed with water, alcohol or other solvent and dried.
  • halide or phenoxide end groups can optionally be reacted by introducing a phenoxide or halide end-capping agent that forms a stable end group.
  • the polymer electrolyte membrane, catalyst layer-covered electrolyte membrane, and membrane electrode assembly of the present invention have excellent chemical stability that can withstand a strong oxidizing atmosphere during fuel cell operation, and are excellent under low humidification conditions. Since any one of these has proton conductivity, excellent mechanical strength, and physical durability, a polymer electrolyte fuel cell that can be stably operated for a long period of time is obtained.
  • the use of the polymer electrolyte fuel cell using the polymer electrolyte composition or polymer electrolyte membrane of the present invention is not particularly limited, but a mobile power supply source is preferable.
  • mobile devices such as mobile phones, personal computers, PDAs, televisions, radios, music players, game machines, headsets, DVD players, human-type and animal-type robots for industrial use, home appliances such as cordless vacuum cleaners, and toys , Electric bicycles, motorcycles, automobiles, buses, trucks and other vehicles and ships, power supplies for mobiles such as railways, stationary primary generators such as stationary generators, or alternatives to these It is preferably used as a hybrid power source.
  • Ion exchange capacity It measured by the neutralization titration method by the following procedures. The measurement was performed 3 times and the average value was taken.
  • 50 mL of a 5 wt% aqueous sodium sulfate solution was added to the electrolyte, and the mixture was allowed to stand for 12 hours for ion exchange.
  • the generated sulfuric acid was titrated using 0.01 mol / L sodium hydroxide aqueous solution.
  • Ion exchange capacity [Concentration of sodium hydroxide aqueous solution (mmol / ml) ⁇ Drip amount (ml)] / Dry weight of sample (g) (2) Number average molecular weight, weight average molecular weight The number average molecular weight and the weight average molecular weight of the polymer were measured by GPC. Tosoh's HLC-8022GPC is used as an integrated UV detector and differential refractometer, and two Tosoh TSK gel Super HM-Hs (inner diameter 6.0 mm, length 15 cm) are used as GPC columns.
  • a 100 nm-thick flake was cut at room temperature using an ultramicrotome, and the obtained flake was collected on a Cu grid and subjected to TEM observation. Observation was carried out at an acceleration voltage of 100 kV, and photography was carried out so that the photographic magnifications were ⁇ 8,000, ⁇ 20,000, and ⁇ 100,000.
  • TEM H7100FA manufactured by Hitachi, Ltd.
  • Concentration (% by weight) of compound (B) having an azole ring 100 ⁇ [average nitrogen content in domain (% by weight) ⁇ polymer nitrogen content (% by weight)] / [Nitrogen content (% by weight) of compound (B) having an azole ring-polymer nitrogen content (% by weight)]
  • the amount of polymer nitrogen and the amount of nitrogen in the compound (B) having an azole ring are the amounts of nitrogen contained in the polymer electrolyte and the compound (B) having an azole ring, respectively.
  • phase separation structure mainly composed of compound (B) having azole ring during formation of sea / island structure
  • the following method is used.
  • the distribution of the compound (B) having an azole ring was measured.
  • elemental analysis is performed at 50 points of the island phase in the sea / island structure to determine the average nitrogen amount in the island phase, and the content of the compound (B) having an azole ring in the island phase is determined in the same manner as in the item (a). Asked. At this time, when the content of the compound (B) having an azole ring was 50% or more, the island phase was determined to be composed mainly of the compound (B) having an azole ring.
  • Synthesis example 3 (Synthesis of oligomer a1 ′ not containing an ionic group represented by the following general formula (G3))
  • G3 an ionic group represented by the following general formula (G3)
  • 25.8 g (100 mmol) of K-DHBP obtained in Synthesis Example 1 and 4,4 20.3 g of '-difluorobenzophenone (Aldrich reagent, 93 mmol) was added, purged with nitrogen, dehydrated at 160 ° C in 300 mL of N-methylpyrrolidone (NMP) and 100 mL of toluene, heated to remove toluene, 180 ° C For 1 hour. Purification was performed by reprecipitation with a large amount of methanol to obtain an oligomer a1 (terminal hydroxyl group) containing no
  • M represents Na or K.
  • the block copolymer b1 contains 50 mol% of the structural units represented by the general formulas (S1) and (S2) as a segment (A1) containing an ionic group and a segment (A2) containing no ionic group, It contained 100 mol%.
  • the block copolymer b1 itself is a polymer electrolyte membrane
  • the ion exchange capacity obtained from neutralization titration is 1.8 meq / g
  • Synthesis example 4 (Synthesis of a polyethersulfone (PES) block copolymer precursor b2 ′ comprising a segment represented by the following formula (G6) and a segment represented by the following formula (G7)) 1.62 g of anhydrous nickel chloride and 15 mL of dimethyl sulfoxide were mixed and adjusted to 70 ° C. To this, 2.15 g of 2,2′-bipyridyl was added and stirred at the same temperature for 10 minutes to prepare a nickel-containing solution.
  • PES polyethersulfone
  • the reaction mixture was added to 60 mL of methanol, and then 60 mL of 6 mol / L hydrochloric acid was added and stirred for 1 hour.
  • the precipitated solid was separated by filtration and dried to obtain 1.62 g of a block copolymer b2 ′ containing segments represented by the following formula (G6) and the following formula (G7) of grayish white with a yield of 99%. .
  • the weight average molecular weight was 230,000.
  • Synthesis example 5 (Synthesis of PES block copolymer b2 composed of a segment represented by the formula (G7) and a segment represented by the following formula (G8)) Add 0.23 g of the block copolymer precursor b2 ′ obtained in Synthesis Example 4 to a mixed solution of 0.16 g of lithium bromide monohydrate and 8 mL of N-methyl-2-pyrrolidone, and react at 120 ° C. for 24 hours. I let you. The reaction mixture was poured into 80 mL of 6 mol / L hydrochloric acid and stirred for 1 hour. The precipitated solid was separated by filtration.
  • the separated solid was dried to obtain a block copolymer b2 composed of a gray-white segment represented by the formula (G7) and a segment represented by the following formula (G8).
  • the resulting polyarylene had a weight average molecular weight of 190,000.
  • the ion exchange capacity obtained from neutralization titration was 2.0 meq / g.
  • the resulting reaction solution was allowed to cool and then diluted by adding 100 mL of toluene.
  • the precipitate of the inorganic compound produced as a by-product was removed by filtration, and the filtrate was put into 2 L of methanol.
  • the precipitated product was separated by filtration, collected, dried, and then dissolved in 250 mL of tetrahydrofuran. This was reprecipitated in 2 L of methanol to obtain 107 g of the target oligomer a3.
  • the number average molecular weight of the oligomer a3 was 7,600.
  • reaction solution was slowly poured onto 1000 g of crushed ice and extracted with ethyl acetate, the organic layer was washed with brine and dried over magnesium sulfate, and then ethyl acetate was distilled off to obtain pale yellow crude crystals 3 -(2,5-Dichlorobenzoyl) benzenesulfonic acid chloride was obtained, and the crude crystals were used without purification in the next step.
  • the reaction system was heated with stirring (finally heated to 82 ° C.) and reacted for 3 hours. An increase in viscosity in the system was observed during the reaction.
  • the polymerization reaction solution was diluted with 175 mL of DMAc, stirred for 30 minutes, and filtered using Celite as a filter aid. With a 1 L three-neck equipped with a stirrer, 24.4 g (281 mmol) of lithium bromide was added to the filtrate in 1/3 portions at 1 hour intervals at 120 ° C. for 5 hours under a nitrogen atmosphere. Reacted. After the reaction, the mixture was cooled to room temperature, poured into 4 L of acetone and solidified.
  • the coagulum was collected by filtration, air-dried, pulverized with a mixer, and washed with 1500 mL of 1N sulfuric acid while stirring. After filtration, the product was washed with ion exchanged water until the pH of the washing solution reached 5 or higher, and then dried at 80 ° C. overnight to obtain 38.0 g of the target block copolymer b3.
  • the weight average molecular weight of this block copolymer was 180,000.
  • the ion exchange capacity determined from neutralization titration was 2.5 meq / g.
  • Example 1 (Preparation of PBI and cobalt-added films) 20 g of the block copolymer b1 obtained in Synthesis Example 3 was dissolved in 80 g of NMP. To this solution, 200 mg of PBI obtained in Synthesis Example 9 and 200 mg of cobalt fine particles (manufactured by Aldrich) were mixed, and stirred at 20,000 rpm for 3 minutes with a stirrer to obtain a transparent solution having a polymer concentration of 20% by mass. . The obtained solution was filtered under pressure using a glass fiber filter, cast on a glass substrate, dried at 100 ° C. for 4 hours, heat-treated at 150 ° C.
  • This membrane electrode assembly was set in an evaluation cell, and while maintaining the temperature at 80 ° C., hydrogen gas was allowed to flow at 400 mL / min on the anode side and air gas at 400 mL / min on the cathode side.
  • a water bubbling system is used for gas humidification, and both hydrogen gas and air gas are humidified at 30 ° C. and supplied to the cell, and the current-voltage curve is measured, and the voltage at a current value of 1 A / cm 2 is compared. The power generation performance was measured.
  • a membrane electrode assembly was prepared by the same method as the power generation performance, set in an evaluation cell, and low humidified hydrogen (70 mL / min, back pressure 0.1 MPaG) and air (174 mL / min, back pressure 0. 05 MPaG) was introduced into the cell, and an accelerated deterioration test was performed in an open circuit.
  • Example 2 A polymer electrolyte membrane f2 was produced in the same manner as in Example 1 except that the amount of PBI and cobalt added was 3 g.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 3 A polymer electrolyte membrane f3 was produced in the same manner as in Example 1 except that the amount of PBI and cobalt added was 4 mg.
  • Example 4 (Preparation of PBI-added film) 20 g of the block copolymer b1 obtained in Synthesis Example 3 was dissolved in 80 g of NMP. To this solution, 200 mg of PBI obtained in Synthesis Example 9 was mixed and stirred with a stirrer at 20,000 rpm for 3 minutes to obtain a transparent solution having a polymer concentration of 20% by mass. The obtained solution was filtered under pressure using a glass fiber filter, cast on a glass substrate, dried at 100 ° C. for 4 hours, heat-treated at 150 ° C. for 10 minutes under nitrogen, and subjected to a polyketal ketone membrane (membrane). A thickness of 15 ⁇ m) was obtained. The solubility of the polymer was very good.
  • the polymer electrolyte membrane f4 was obtained by immersing in a large excess amount of pure water for 24 hours and thoroughly washing.
  • the coating amount was set to 0.50 mg / cm 2 for both the Pt carrying amount and the polymer carrying amount.
  • the catalyst sheet c1 having a size of 5 cm ⁇ 5 cm and a thickness of about 10 ⁇ m was obtained by drying at room temperature for 1 hour and in air at 120 ° C. for 1 hour.
  • platinum-cobalt alloy (Ru: 50 mass%) nanoparticles (average particle diameter: 2 nm, specific surface area: 100 to 200 cm 2 / mg) were supported: 36 mass. % was highly dispersed in carbon fine particles.
  • Pt and Co catalyst sheet c2 were obtained in the same manner as the catalyst sheet c1 except that 0.5 g of Pt supported carbon and 0.5 g of Pt / Co alloy supported carbon were used instead of 1 g of Pt supported carbon.
  • the catalyst sheet c1 was an anode catalyst layer
  • the catalyst sheet c2 was a cathode catalyst layer.
  • a carbon electrode (ELAT (registered trademark) B-1 manufactured by DE NORA AMERICA, USA) is set as a gas diffusion layer (GDL) on both sides of the MEA (the outer surfaces of the anode catalyst layer and the cathode catalyst layer).
  • GDL gas diffusion layer
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, and the initial voltage was compared with the voltage at the time when 7000 hours passed. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 5 (Production of catalyst layer-coated electrolyte membrane including cobalt-containing anode and membrane electrode composite)
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 4 except that the catalyst sheet c1 was a cathode catalyst layer and the catalyst sheet c2 was an anode catalyst layer.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 6 (Production of cobalt fine particle coating film)
  • the polymer electrolyte membrane f4 (size 7 cm ⁇ 7 cm) produced in Example 4 was coated with 200 mg of cobalt fine particle 15% by weight aqueous dispersion (cobalt fine particles produced by Aldrich were dispersed in ultrapure water). .
  • the coating film f5 having a size of 7 cm ⁇ 7 cm was obtained by drying at room temperature for 1 hour and in air at 120 ° C. for 1 hour.
  • a catalyst layer-coated electrolyte membrane and a membrane electrode composite were prepared in the same manner as in Example 4 except that a cobalt coating membrane f5 was used instead of the polymer electrolyte membrane f4, and the catalyst sheet c1 was used as both the cathode and anode catalyst layers. Produced.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. At this time, the cobalt-coated surface was used as a cathode for evaluation. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 7 (Production of cobalt-coated GDL) A carbon cloth of 5 cm ⁇ 5 cm (ELAT (registered trademark) B-1 manufactured by DE NORA NORTH AMERICA, USA) having a dispersion of 100 mg of cobalt fine particles in an amount of 100 mg (cobalt fine particles manufactured by Aldrich Co., dispersed in ultrapure water) ) was applied. After coating, drying was performed at room temperature for 1 hour and in air at 120 ° C. for 1 hour to obtain a cobalt-coated GDL gas diffusion layer g1 having a size of 5 cm ⁇ 5 cm. Catalyst sheet c1 was a catalyst layer for both cathode and anode. In the same manner as in Example 4 except that the anode gas diffusion layer was changed to g1, a catalyst layer-coated electrolyte membrane and a membrane electrode assembly were produced.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 8 (Preparation of PBI, cobalt acetylacetonate complex-added film) A polymer electrolyte membrane f6 was produced in the same manner as in Example 1, except that 200 mg of tris (acetylacetonato) cobalt (manufactured by Aldrich) was used instead of 1 g of the cobalt fine particle 20 wt% aqueous dispersion.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 1 except that the polymer electrolyte membrane f6 was used instead of the polymer electrolyte membrane f1.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 9 (Preparation of PBI, cobalt nitrate added film) 0.480 g of cobalt (II) nitrate hexahydrate (manufactured by Aldrich) was dissolved in pure water to prepare 30 L of a 55 ⁇ mol / L cobalt (II) nitrate solution. 20 g of the polymer electrolyte membrane f4 produced in Example 4 was immersed in this solution for 72 hours, and a polymer electrolyte membrane f7 incorporating cobalt ions was obtained by ion exchange with sulfonic acid groups.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 10 (Production of phthalocyanine and cobalt-added films) A polymer electrolyte membrane f8 was produced in the same manner as in Example 1 except that 200 mg of phthalocyanine (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 200 mg of PBI.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 1 except that the polymer electrolyte membrane f8 was used instead of the polymer electrolyte membrane f1.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 11 (Preparation of NRE211CS-based cobalt-containing catalyst layer-coated electrolyte membrane, membrane electrode composite) A polymer electrolyte membrane f9 was produced in the same manner as in Example 4 except that 20 g of NRE211CS, which is a kind of Nafion (registered trademark), was used instead of 20 g of the block copolymer b1.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 5 except that the polymer electrolyte membrane f9 was used instead of the polymer electrolyte membrane f4.
  • Example 12 (Preparation of PES block copolymer-based cobalt-containing catalyst layer-coated electrolyte membrane, membrane electrode composite) A polymer electrolyte membrane f10 was produced in the same manner as in Example 1 except that the PES block copolymer b2 obtained in Synthesis Example 5 was used instead of the block copolymer b1.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 1 except that the polymer electrolyte membrane f10 was used instead of the polymer electrolyte membrane f1.
  • a membrane electrode assembly was prepared in the same manner as the power generation performance described in Example 1, set in an evaluation cell, and kept at 80 ° C. while maintaining low humidity in hydrogen (70 mL / min, back pressure 0.1 MPaG). Air (174 mL / min, back pressure 0.05 MPaG) was introduced into the cell, and an accelerated deterioration test was performed in an open circuit. After operating the fuel cell under these conditions for 1000 hours, the membrane electrode assembly was taken out, put into a mixed solution of ethanol / water, and further subjected to ultrasonic treatment to remove the catalyst layer.
  • Example 13 (Preparation of polyarylene block copolymer-based cobalt-containing catalyst layer-coated electrolyte membrane, membrane electrode composite) A polymer electrolyte membrane f11 was produced in the same manner as in Example 1 except that the polyarylene block copolymer b3 obtained in Synthesis Example 8 was used instead of the block copolymer b1.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 1 except that the polymer electrolyte membrane f11 was used instead of the polymer electrolyte membrane f1.
  • Example 14 (Preparation of PBI, ruthenium-added film)
  • Example 1 except that 1 g of a 20% by weight aqueous dispersion of ruthenium fine particles (manufactured by Strem, particle size ⁇ 20 nm, concentrated 500 mg / L, ruthenium content 200 mg) was added instead of 200 mg of cobalt fine particles.
  • ruthenium fine particles manufactured by Strem, particle size ⁇ 20 nm, concentrated 500 mg / L, ruthenium content 200 mg
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 15 A polymer electrolyte membrane f13 was produced in the same manner as in Example 14 except that the amount of PBI and ruthenium added was 3 g.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 16 A polymer electrolyte membrane f14 was produced in the same manner as in Example 14 except that the amount of PBI and ruthenium added was changed to 4 mg.
  • Example 17 (Preparation of Pt and Ru-containing catalyst sheet) Pt, Ru catalyst sheet c3 in the same manner as the catalyst sheet c1, except that Pt, Ru supported carbon (TEC66E50, Pt 25 wt%, Ru 25 wt% manufactured by Tanaka Kikinzoku Co., Ltd.) was used instead of Pt supported carbon. Got.
  • a catalyst layer-covered electrolyte membrane and membrane electrode composite containing ruthenium-containing cathode were produced in the same manner as in Example 4 except that the catalyst sheet c3 was used instead of the catalyst sheet c2.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 18 (Preparation of catalyst layer-covered electrolyte membrane including a ruthenium-containing anode and membrane electrode composite) A catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 17 except that the catalyst sheet c1 was a cathode catalyst layer and the catalyst sheet c3 was an anode catalyst layer.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 19 (Preparation of ruthenium fine particle coating film) Ruthenium fine particle 15 wt% aqueous dispersion 200 mg (manufactured by Strem, concentrated particle size ⁇ 20 nm, concentration 500 mg / L) on the polymer electrolyte membrane f4 (size 7 cm ⁇ 7 cm) produced in Example 4, amount of ruthenium 30 mg) was applied. After the application, the ruthenium coating film f15 having a size of 7 cm ⁇ 7 cm was obtained by drying at room temperature for 1 hour and in air at 120 ° C. for 1 hour.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were prepared in the same manner as in Example 4 except that a ruthenium coating film f15 was used instead of the polymer electrolyte membrane f4, and the catalyst sheet c1 was used as both the cathode and anode catalyst layers. Produced.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. At this time, the ruthenium-coated surface was evaluated as an anode. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 20 (Production of ruthenium-coated GDL) 5 mg ⁇ 5 cm carbon cloth (ELAT (registered trademark) B-1 manufactured by DE NORA NORTH AMERICA, USA) was concentrated with 100 mg of a ruthenium fine particle 15% by weight aqueous dispersion (manufactured by Strem, particle size ⁇ 20 nm, concentration 500 mg / L). A ruthenium amount of 10 mg) was applied. After coating, drying was performed at room temperature for 1 hour and in air at 120 ° C. for 1 hour to obtain a ruthenium-coated GDL gas diffusion layer g2 having a size of 5 cm ⁇ 5 cm.
  • ELAT registered trademark
  • aqueous dispersion manufactured by Strem, particle size ⁇ 20 nm, concentration 500 mg / L
  • a ruthenium amount of 10 mg was applied. After coating, drying was performed at room temperature for 1 hour and in air at 120 ° C. for 1 hour to obtain a ruthenium-coated
  • Catalyst sheet c1 was a catalyst layer for both cathode and anode Then, a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 4 except that the gas diffusion layer of the anode was changed to g2.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, and the initial voltage was compared with the voltage at the time when 7000 hours passed. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 21 (Preparation of PBI, ruthenium acetylacetonate complex-added film) A polymer electrolyte membrane f16 was produced in the same manner as in Example 1, except that 200 mg of tris (acetylacetonato) ruthenium (manufactured by Aldrich) was used instead of 1 g of the ruthenium fine particle 20 wt% aqueous dispersion.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 1 except that the polymer electrolyte membrane f16 was used instead of the polymer electrolyte membrane f1.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 22 (Production of phthalocyanine and ruthenium-added films) A polymer electrolyte membrane f17 was produced in the same manner as in Example 1 except that 200 mg of phthalocyanine (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 200 mg of PBI.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 1 except that the polymer electrolyte membrane f17 was used instead of the polymer electrolyte membrane f1.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 23 (Preparation of NRE211CS-based ruthenium-containing catalyst layer-coated electrolyte membrane, membrane electrode composite) A catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 11 except that the catalyst sheet c3 was used instead of the catalyst sheet c2.
  • Example 24 (Preparation of PES block copolymer-based catalyst layer-coated electrolyte membrane, membrane electrode composite) A polymer electrolyte membrane f18 was produced in the same manner as in Example 14 except that the PES block copolymer b2 obtained in Synthesis Example 5 was used instead of the block copolymer b1.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 1 except that the polymer electrolyte membrane f18 was used instead of the polymer electrolyte membrane f1.
  • a membrane electrode assembly was prepared in the same manner as the power generation performance described in Example 1, set in an evaluation cell, and kept at 80 ° C. while maintaining low humidity in hydrogen (70 mL / min, back pressure 0.1 MPaG). Air (174 mL / min, back pressure 0.05 MPaG) was introduced into the cell, and an accelerated deterioration test was performed in an open circuit. After operating the fuel cell under these conditions for 1000 hours, the membrane electrode assembly was taken out, put into a mixed solution of ethanol / water, and further subjected to ultrasonic treatment to remove the catalyst layer.
  • Example 25 (Preparation of polyarylene block copolymer-based catalyst layer-coated electrolyte membrane, membrane electrode composite) A polymer electrolyte membrane f19 was produced in the same manner as in Example 1 except that the polyarylene block copolymer b3 obtained in Synthesis Example 8 was used instead of the block copolymer b1.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 1 except that the polymer electrolyte membrane f19 was used instead of the polymer electrolyte membrane f1.
  • Example 26 (PBI, production of silver-added film)
  • Example 1 except that 1 g of silver fine particle 20 wt% aqueous dispersion (manufactured by Strem, particle size ⁇ 20 nm, concentrated 500 mg / L, silver amount 200 mg) was added instead of 200 mg of cobalt fine particles.
  • a polymer electrolyte membrane f20 was manufactured.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 27 (Preparation of PBI, palladium-added film) Except for adding 200 mg of cobalt fine particles, 1 g of palladium fine particle 20 wt% aqueous dispersion (manufactured by Strem, particle size ⁇ 20 nm, concentrated 500 mg / L, palladium amount 200 mg) was added in the same manner as in Example 1. Thus, a polymer electrolyte membrane f21 was manufactured.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 28 (Preparation of PBI, palladium nitrate-added film) A polymer electrolyte membrane f22 was produced in the same manner as in Example 9, except that 0.380 g of palladium (II) nitrate was added instead of 0.480 g of cobalt nitrate hexahydrate.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • Example 29 (Preparation of PBI, rhodium-added film) Except for adding 200 mg of cobalt fine particles, 1 g of a 20 wt% aqueous dispersion of rhodium fine particles (manufactured by Strem, particle size ⁇ 20 nm, concentrated 500 mg / L, rhodium content 200 mg) was added in the same manner as in Example 1. Thus, a polymer electrolyte membrane f23 was manufactured.
  • Example 1 Since the obtained film was insoluble in NMP and the molecular weight retention rate could not be measured, the power generation performance and chemical durability were evaluated in the same manner as in Example 1. As in Example 1, the open circuit voltage did not drop below 0.7V even after 7000 hours had passed, so the evaluation was terminated, the initial voltage was compared with the voltage at the 7000 hour point, and the chemical durability of the electrolyte membrane was measured as the voltage holding ratio. Sex was evaluated. Separately, the ion exchange capacity of the electrolyte membrane was measured, and the results are shown in Table 1.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 1 except that the polymer electrolyte membrane f1 'was used instead of the polymer electrolyte membrane f1.
  • Example 2 A polymer electrolyte membrane f2 ′ was produced in the same manner as in Example 1 except that no cobalt fine particles were used.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 1 except that the polymer electrolyte membrane f2 'was used instead of the polymer electrolyte membrane f1.
  • Example 3 A polymer electrolyte membrane f3 ′ was produced in the same manner as in Example 1 except that PBI was not used.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 1 except that the polymer electrolyte membrane f3 'was used instead of the polymer electrolyte membrane f1.
  • Example 4 A catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Example 5 except that the polymer electrolyte membrane f1 ′ was used instead of the polymer electrolyte membrane f4.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Comparative Example 1 except that the polymer electrolyte membrane f4 'was used instead of the polymer electrolyte membrane f1'.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Comparative Example 1 except that the polymer electrolyte membrane f5 'was used instead of the polymer electrolyte membrane f1'.
  • a catalyst layer-covered electrolyte membrane and a membrane electrode assembly were produced in the same manner as in Comparative Example 1 except that the polymer electrolyte membrane f6 'was used instead of the polymer electrolyte membrane f1'.
  • Examples 1 to 10 and 14 to 22 in which polymer electrolyte membranes, catalyst layer-covered electrolyte membranes and membrane electrode composites containing a compound (B) having an azole ring and a transition metal-containing additive (C) were prepared. And the open circuit retention times of 26 to 29 are Comparative Example 1 in which no additive was added, Comparative Example 2 in which only the compound (B) having an azole ring was added, Comparative Example 3 in which only the transition metal-containing additive was added, and Comparative Example It was longer than Example 4.
  • Examples 11 and 23 with Comparative Example 5, Examples 12 and 24 with Comparative Example 6, Examples 13 and 25 with Comparative Example 7, a compound (B) having an azole ring and a transition metal-containing additive ( The addition of C) was superior in open circuit retention time or molecular weight retention.
  • the polymer electrolyte membrane, the catalyst layer-covered electrolyte membrane, and the membrane electrode assembly containing the compound (B) having an azole ring and the transition metal-containing additive (C) are produced by hydrogen peroxide generated by power generation of the fuel cell. Or it was shown that the thing which can provide the outstanding durability with respect to a hydroxyl radical.
  • the polymer electrolyte composition and polymer electrolyte membrane of the present invention can be applied to various electrochemical devices (for example, fuel cells, water electrolysis devices, chloroalkali electrolysis devices, hydrogen compression devices, redox flow batteries, etc.).
  • electrochemical devices for example, fuel cells, water electrolysis devices, chloroalkali electrolysis devices, hydrogen compression devices, redox flow batteries, etc.
  • it is suitable for a fuel cell, and particularly suitable for a fuel cell using hydrogen as a fuel.
  • Applications of the polymer electrolyte fuel cell of the present invention are not particularly limited, but are portable devices such as mobile phones, personal computers, PDAs, video cameras, digital cameras, home appliances such as cordless vacuum cleaners, toys, electric bicycles, automatic It is preferably used as a power supply source for vehicles such as motorcycles, automobiles, buses, trucks, etc., moving bodies such as ships, railways, etc., conventional primary batteries such as stationary generators, alternatives to secondary batteries, or hybrid power sources with these. .

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Abstract

L'objectif de la présente invention est de pourvoir : à une composition d'électrolyte polymère excellente en pratique qui possède une excellente stabilité chimique qui peut résister à une atmosphère fortement oxydante pendant le fonctionnement d'une pile à combustible, tout en assurant une excellente conductivité protonique dans des conditions de faible humidification, une excellente résistance mécanique et une excellente durabilité physique ; à une membrane électrolytique polymère qui utilise cette composition d'électrolyte polymère ; à un ensemble membrane-électrodes ; et à une pile à combustible à électrolyte polymère solide. Une composition d'électrolyte polymère est décrite qui contient (A) un polymère contenant un groupe ionique, (B) un composé contenant un cycle azole et (C) un additif contenant un métal de transition, le métal de transition étant composé d'un ou de plusieurs métaux choisis dans le groupe constitué par le cobalt, le nickel, le ruthénium, le rhodium, le palladium, l'argent et l'or.
PCT/JP2015/059661 2014-03-31 2015-03-27 Composition d'électrolyte polymère, membrane électrolytique polymère l'utilisant, membrane électrolytique revêtue d'une couche de catalyseur, ensemble membrane-électrodes et pile à combustible à électrolyte polymère solide WO2015152058A1 (fr)

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EP15774165.3A EP3128592B1 (fr) 2014-03-31 2015-03-27 Composition d'électrolyte polymère, membrane électrolytique polymère l'utilisant, membrane électrolytique revêtue d'une couche de catalyseur, ensemble membrane-électrodes et pile à combustible à électrolyte polymère solide
KR1020167028592A KR102282248B1 (ko) 2014-03-31 2015-03-27 고분자 전해질 조성물, 및 이것을 이용한 고분자 전해질막, 촉매층 피복 전해질막, 막 전극 복합체 및 고체 고분자형 연료 전지
JP2015519115A JP6610252B2 (ja) 2014-03-31 2015-03-27 高分子電解質組成物、ならびに、それを用いた高分子電解質膜、触媒層被覆電解質膜、膜電極複合体および固体高分子型燃料電池
US15/301,018 US10253147B2 (en) 2014-03-31 2015-03-27 Polymer electrolyte composition, polymer electrolyte membrane using same, catalyst coated membrane, membrane electrode assembly and polymer electrolyte fuel cell
CN201580017524.4A CN106133976B (zh) 2014-03-31 2015-03-27 高分子电解质组合物、使用其的高分子电解质膜、被覆催化剂层的电解质膜、膜电极复合体
CA2944372A CA2944372C (fr) 2014-03-31 2015-03-27 Composition d'electrolyte polymere, membrane electrolytique polymere l'utilisant, membrane electrolytique revetue d'une couche de catalyseur, ensemble membrane-electrodes et pile a combustible a electrolyte polymere solide

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JP2014071762 2014-03-31
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JP7162154B1 (ja) * 2021-07-14 2022-10-27 日本碍子株式会社 電気化学セル用電解質膜

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EP3128592A1 (fr) 2017-02-08
JP6610252B2 (ja) 2019-11-27
KR102282248B1 (ko) 2021-07-27
CN106133976B (zh) 2019-11-29
TWI658087B (zh) 2019-05-01
US20170037207A1 (en) 2017-02-09
US10253147B2 (en) 2019-04-09
CN106133976A (zh) 2016-11-16
TW201546154A (zh) 2015-12-16
EP3128592B1 (fr) 2021-03-17
CA2944372C (fr) 2022-08-09

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